A clickable alkyne monomer, PgMA, was successfully polymerized in a well-controlled manner via single electron transfer initiation and propagation through the radical addition fragmentation chain transfer (SET-RAFT) method. The living nature of the polymerization was confirmed by the first-order kinetic plots, the linear relationships between molecular weights and the monomer conversions while keeping relatively narrow (M-w) over bar/(M-n) over bar (<= 1.55), and the successful chain-extension with MMA. The better controllability of SET-RAFT than other CRP methods is attributed to the less competitive termination in view of the presence of the CTA as well as the Cu(II) that is generated in situ. Moreover, a one-pot/one-step technique combining SET-RAFT and "click chemistry" methods has been successfully employed to prepare the side-chain functionalized polymers.